Method development for trace determination of poly(naphthalenesulfonate)-type pollutants in water by liquid chromatography–electrospray mass spectrometry

A very sensitive analytical procedure based on LC–MS for determining trace amounts of the more relevant poly(naphthalenesulfonate) (PNS) contaminants present in environmental waters is presented. Extraction was performed on a styrene–divinylbenzene copolymer resin solid-phase extraction cartridge after addition of ammonium acetate to the sample. Small amounts of ammonium acetate in the mobile phase allowed the determination and characterisation of the four shorter oligomers by liquid chromatography–electrospray mass spectrometry. Under such conditions the electrospray process generates fully ionised molecules which greatly simplifies interpretation of spectra and quantitation. Additionally, confirmatory ions can be generated by the in-source collision-induced decomposition process. The effectiveness of the method was assessed in recovery experiments from drinking and river water samples spiked with commercial mixtures of PNS concrete plasticizers also referred as naphthalenesulfonate–formaldehyde condensates. Moreover, the performance of this method was compared to methods using ion-pair chromatography coupled with fluorimetric and mass spectrometric detection. Method detection limits were in the low picomolar range (1 ng/l for the monomer) for each isomer. In order to evaluate the environmental relevance of PNS type compounds waste, river and ground water grab samples were analysed. Concentrations of PNS oligomers detected in these samples ranged between 53 ng/l and 32 μg/l.